US2558923A - Process of purifying ethylene diamine di-acetic acid - Google Patents

Process of purifying ethylene diamine di-acetic acid Download PDF

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US2558923A
US2558923A US26727A US2672748A US2558923A US 2558923 A US2558923 A US 2558923A US 26727 A US26727 A US 26727A US 2672748 A US2672748 A US 2672748A US 2558923 A US2558923 A US 2558923A
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ethylene diamine
acetic acid
solution
sodium sulfate
acid
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US26727A
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Frederick C Bersworth
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
    • C07C227/14—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton from compounds containing already amino and carboxyl groups or derivatives thereof
    • C07C227/18—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton from compounds containing already amino and carboxyl groups or derivatives thereof by reactions involving amino or carboxyl groups, e.g. hydrolysis of esters or amides, by formation of halides, salts or esters
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
    • C07C227/38—Separation; Purification; Stabilisation; Use of additives
    • C07C227/40—Separation; Purification
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/02—Preparation of carboxylic acids or their salts, halides or anhydrides from salts of carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/41—Preparation of salts of carboxylic acids
    • C07C51/412—Preparation of salts of carboxylic acids by conversion of the acids, their salts, esters or anhydrides with the same carboxylic acid part

Definitions

  • This invention relates to chemical processes and has for its object the provision of a method for producing ethylene diamine di-ace'tic acid.
  • Another object is to provide the product ethyl ene diamine di-acetic acid.
  • a method of producing ethylene diamine di-acetic acid which comprises condensing sodium cyanide and formaldehyde in approximately equal molar weight proportions in an aqueous solution of ethylene diamine containing sodium hydroxide sufficient to provide a pH of 8.5l0.5 while maintaining a reaction temperature of about 90 C. or within the range 85 to 95 C., and While excluding atmospheric gases from contact with the reaction solution in accordance with the general process described and claimed in my Patent No. 2,387,735 issued October 30, 1945, limiting the condensing reacting weights of the sodium-cyanide and formaldehyde added to the reaction solution to two molar reacting weights of each for each molar weight of ethylene diamine present in the reaction solution.
  • the amount of water present in the reaction solution is calculated to provide together with the water added during the reaction along with the sodium cyanide and formaldehyde a final solution containing about 20% dissolved solids which should consist substantially of the alkali metal salt (sodium) of ethylene diamine di-acetic acid and an excess of sodium hydroxide approximately sufiicient to provide a pH in solution of from 8.5 to 10.5.
  • This alkaline reaction solution is filtered while hot and is allowed to cool to atmospheric temperatures and is then neutralized while agitated sumcient to maintain a uniform distribution of compounds therein with dilute solution of sulfuric acid until a pH of about 6.5 is obtained in the solution.
  • This acid pH solution is then subjected to distillation under reduced pressure to reduce the volume of the solution sufficiently to precipitate out of solution the major portion of the sodium sulfate present therein which precipitated sulfate is removed by filtration.
  • the filtrate is subjected to a succession of distillation steps under reduced pressure, and filtration steps to separate therefrom the major portion of the remaining sodium sulfate present in the filtrate during which practice the sodium sulfate recovered is tested for the presence of organic salts therein by known tests and any such organic salts foundtherein are recoveredtherefrom by digesting the precipitated sodium sulfate with a small volume of water sufiicient to dissolve completely the organic salt and only slightly the sodium sulfate, which solution after filtering is returned to the filtrate under treat ment for further distillation.
  • the removal of sodium sulfate by this practice is continued until the viscosity of the mother liquor filtrate becomes such as to make filtration difficult.
  • the total amount of sodium sulfate collected is Weighed and the percentage recovery determined by calculation against the known weight of sulfuric acid added originally to the reaction solution.
  • the percent recovery of sodium sulfate by this practice should at least approximate and may be as high as under best conditions.
  • the viscous mother liquor filtrate is then mixed thoroughly with an equal volume of ethyl alcohol and is allowed to stand for a sufiicient time interval to permit the separation therefrom of the ethylene diamine di-acetic acid as a fine white crystal product which slowly collects in the bottom of the container.
  • the crystals After decanting or otherwise separating the major portion of the supernatant alcoholic aqueous liquid from the deposited crystals, the crystals are redissolved in the smallest necessary amount of water again diluted with an equal volume of ethyl alcohol and permitted to recrystallize.
  • recrystallization treatments may be required to obtain finally a sodium sulfate-free final crystallized product.
  • the ethylene diamine di-acetic acid product obtained by the practice of the present invention is highly utilizable in the art of organic synthesis as an intermediate reaction product in the forming of a large number of amino compounds.
  • the acid is reactive as a weak acid with basic compounds to form salts and the metallic salts of the acid are strong baseexchange agents with other metallic salts the basic ion of which is a stronger base than that neutralizing the carboxylic groups of the diacetic acid.
  • the di-metal salts of ethylene diamine di-acetic acid evidence unusual properties in the forming of complexes, particularly with poly-valent metal ions, some of which are ionic and others of which are non-ionic, some of which complexes appear to be of the chelate-type, others of the Werner-type and still others a combination chelate-Werner type of complex which have wide potential utility in the art of chemistry.
  • the method of treating an aqueous solution containing the sodium salt of ethylene diamine diacetic acid and sodium hydroxide to recover the diacetic acid therefrom comprises acidifying the solution with sulfuric acid to a pH of 6.5, removing the water of solution to the extent producing precipitation of the major portion of the sodium sulfate without substantial precipitation of the diacetic acid, removing the precipitated sodium sulfate from the solution and adding ethyl alcohol to the solution in an amount precipitating the diacetic acid without substantial precipitation of the residual sodium sulfate present therein.

Description

Patented July 3, 1951 UNITED PROCESS OF PURIFYINGLETHYLENE DIAMINE DI-ACETIC ACID Frederick C. Berswortli, Verona, N. J
No Drawing. Application May 12, 1948, Serial No. 26.727
1 Claim. (01. 260'534) This invention relates to chemical processes and has for its object the provision of a method for producing ethylene diamine di-ace'tic acid.
Another object is to provide the product ethyl ene diamine di-acetic acid.
Other objects will be apparent as the invention is more fully hereinafter disclosed.
In accordance with these objects I have provided a method of producing ethylene diamine di-acetic acid which comprises condensing sodium cyanide and formaldehyde in approximately equal molar weight proportions in an aqueous solution of ethylene diamine containing sodium hydroxide sufficient to provide a pH of 8.5l0.5 while maintaining a reaction temperature of about 90 C. or within the range 85 to 95 C., and While excluding atmospheric gases from contact with the reaction solution in accordance with the general process described and claimed in my Patent No. 2,387,735 issued October 30, 1945, limiting the condensing reacting weights of the sodium-cyanide and formaldehyde added to the reaction solution to two molar reacting weights of each for each molar weight of ethylene diamine present in the reaction solution.
The amount of water present in the reaction solution is calculated to provide together with the water added during the reaction along with the sodium cyanide and formaldehyde a final solution containing about 20% dissolved solids which should consist substantially of the alkali metal salt (sodium) of ethylene diamine di-acetic acid and an excess of sodium hydroxide approximately sufiicient to provide a pH in solution of from 8.5 to 10.5.
This alkaline reaction solution is filtered while hot and is allowed to cool to atmospheric temperatures and is then neutralized while agitated sumcient to maintain a uniform distribution of compounds therein with dilute solution of sulfuric acid until a pH of about 6.5 is obtained in the solution.
This acid pH solution is then subjected to distillation under reduced pressure to reduce the volume of the solution sufficiently to precipitate out of solution the major portion of the sodium sulfate present therein which precipitated sulfate is removed by filtration.
The filtrate is subjected to a succession of distillation steps under reduced pressure, and filtration steps to separate therefrom the major portion of the remaining sodium sulfate present in the filtrate during which practice the sodium sulfate recovered is tested for the presence of organic salts therein by known tests and any such organic salts foundtherein are recoveredtherefrom by digesting the precipitated sodium sulfate with a small volume of water sufiicient to dissolve completely the organic salt and only slightly the sodium sulfate, which solution after filtering is returned to the filtrate under treat ment for further distillation.
The removal of sodium sulfate by this practice is continued until the viscosity of the mother liquor filtrate becomes such as to make filtration difficult. The total amount of sodium sulfate collected is Weighed and the percentage recovery determined by calculation against the known weight of sulfuric acid added originally to the reaction solution. The percent recovery of sodium sulfate by this practice should at least approximate and may be as high as under best conditions.
The viscous mother liquor filtrate is then mixed thoroughly with an equal volume of ethyl alcohol and is allowed to stand for a sufiicient time interval to permit the separation therefrom of the ethylene diamine di-acetic acid as a fine white crystal product which slowly collects in the bottom of the container. After decanting or otherwise separating the major portion of the supernatant alcoholic aqueous liquid from the deposited crystals, the crystals are redissolved in the smallest necessary amount of water again diluted with an equal volume of ethyl alcohol and permitted to recrystallize. One or more of such recrystallization treatments may be required to obtain finally a sodium sulfate-free final crystallized product.
The ethylene diamine di-acetic acid product obtained by the practice of the present invention is highly utilizable in the art of organic synthesis as an intermediate reaction product in the forming of a large number of amino compounds. In aqueous solutions the acid is reactive as a weak acid with basic compounds to form salts and the metallic salts of the acid are strong baseexchange agents with other metallic salts the basic ion of which is a stronger base than that neutralizing the carboxylic groups of the diacetic acid. The di-metal salts of ethylene diamine di-acetic acid evidence unusual properties in the forming of complexes, particularly with poly-valent metal ions, some of which are ionic and others of which are non-ionic, some of which complexes appear to be of the chelate-type, others of the Werner-type and still others a combination chelate-Werner type of complex which have wide potential utility in the art of chemistry.
According to present chemical theories the ethylene diamine di-acetic acid has the structural formula:
It is believed apparent that the invention may be widely varied without essential departure therefrom and all such modifications and departures are contemplated as may fall within the scope of the following claim:
What I claim is:
The method of treating an aqueous solution containing the sodium salt of ethylene diamine diacetic acid and sodium hydroxide to recover the diacetic acid therefrom which comprises acidifying the solution with sulfuric acid to a pH of 6.5, removing the water of solution to the extent producing precipitation of the major portion of the sodium sulfate without substantial precipitation of the diacetic acid, removing the precipitated sodium sulfate from the solution and adding ethyl alcohol to the solution in an amount precipitating the diacetic acid without substantial precipitation of the residual sodium sulfate present therein.
FREDERICK C. BERSWORTH.
4 REFERENCES CITED The following references are of record in the file of this patent:
UNITED STATES PATENTS Number Name Date 2,085,784 Bottoms July 6, 1937 2,163,594 Engels et a1 June 27, 1939 2,209,299 Schoeller et a1. June 23, 1940 2,334,163 Kirk Nov. 16, 1943 2,387,735 Bersworth Oct. 30, 1945 2,407,645 Bersworth Sept. 17, 1946 2,428,353 Bersworth Oct 7, 1947 FOREIGN PATENTS Number Country Date 638,071 Germany Nov. 9, 1936 482,352 Great Britain Mar. 28, 1938 46,892 Netherlands Oct. 16, 1939 OTHER REFERENCES Foreman, Biochem, J., vol. 8, pp. 463-466 (1914).
Pick et a1., Chem. Abstracts, vol. 31, columns 1043-1044 (1937).
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3988367A (en) * 1975-11-11 1976-10-26 W. R. Grace & Co. Preparation of N,N'-dicarboxymethyl-1,3-propanediamines
JPS5473728A (en) * 1977-11-16 1979-06-13 Daiichi Kagaku Yakuhin Kk Manufacture of ethylene diamineen*n**diacetate
US4200238A (en) * 1977-10-03 1980-04-29 Owens-Illinois, Inc. Method of preparing a rapidly soluble and machine handleable particulate composite and product
US4535167A (en) * 1981-12-14 1985-08-13 Merck & Co. Inc. Chiral, N-protected, N-substituted α-amino acids

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL46892C (en) * 1936-02-15
DE638071C (en) * 1935-04-05 1936-11-09 I G Farbenindustrie Akt Ges Process for the production of polyaminocarboxylic acid nitriles, the corresponding acids or their compounds
US2085784A (en) * 1935-04-29 1937-07-06 Girdler Corp Process of purifying aminated compounds
GB482352A (en) * 1936-09-28 1938-03-28 Ig Farbenindustrie Ag Improvements in the manufacture and production of polyamino carboxylic acids and their derivatives
US2163594A (en) * 1936-12-01 1939-06-27 Merck & Co Inc Process for the production of amino acids
US2209299A (en) * 1936-03-06 1940-07-23 Schering Corp Glutathione compounds and a method of making the same
US2334163A (en) * 1942-06-25 1943-11-16 American Cyanamid Co Preparation of beta-alanine
US2387735A (en) * 1941-07-03 1945-10-30 Martin Dennis Company Method of forming carboxylic amino acids
US2407645A (en) * 1943-06-21 1946-09-17 Martin Dennis Company Aliphatic polycarboxylic amino acids and process of making them
US2428353A (en) * 1943-06-21 1947-10-07 Frederick C Bersworth Lower aliphatic esters of ethylene-and propylene-diamine n,n'-tetracetic acids

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE638071C (en) * 1935-04-05 1936-11-09 I G Farbenindustrie Akt Ges Process for the production of polyaminocarboxylic acid nitriles, the corresponding acids or their compounds
US2085784A (en) * 1935-04-29 1937-07-06 Girdler Corp Process of purifying aminated compounds
NL46892C (en) * 1936-02-15
US2209299A (en) * 1936-03-06 1940-07-23 Schering Corp Glutathione compounds and a method of making the same
GB482352A (en) * 1936-09-28 1938-03-28 Ig Farbenindustrie Ag Improvements in the manufacture and production of polyamino carboxylic acids and their derivatives
US2163594A (en) * 1936-12-01 1939-06-27 Merck & Co Inc Process for the production of amino acids
US2387735A (en) * 1941-07-03 1945-10-30 Martin Dennis Company Method of forming carboxylic amino acids
US2334163A (en) * 1942-06-25 1943-11-16 American Cyanamid Co Preparation of beta-alanine
US2407645A (en) * 1943-06-21 1946-09-17 Martin Dennis Company Aliphatic polycarboxylic amino acids and process of making them
US2428353A (en) * 1943-06-21 1947-10-07 Frederick C Bersworth Lower aliphatic esters of ethylene-and propylene-diamine n,n'-tetracetic acids

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3988367A (en) * 1975-11-11 1976-10-26 W. R. Grace & Co. Preparation of N,N'-dicarboxymethyl-1,3-propanediamines
US4200238A (en) * 1977-10-03 1980-04-29 Owens-Illinois, Inc. Method of preparing a rapidly soluble and machine handleable particulate composite and product
JPS5473728A (en) * 1977-11-16 1979-06-13 Daiichi Kagaku Yakuhin Kk Manufacture of ethylene diamineen*n**diacetate
US4535167A (en) * 1981-12-14 1985-08-13 Merck & Co. Inc. Chiral, N-protected, N-substituted α-amino acids

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